CN100415687C - Aluminum nitride sintered compact - Google Patents

Aluminum nitride sintered compact Download PDF

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Publication number
CN100415687C
CN100415687C CNB038252961A CN03825296A CN100415687C CN 100415687 C CN100415687 C CN 100415687C CN B038252961 A CNB038252961 A CN B038252961A CN 03825296 A CN03825296 A CN 03825296A CN 100415687 C CN100415687 C CN 100415687C
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aluminum nitride
sintered product
nitride sintered
grain
sintering
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CN1701050A (en
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金近幸博
三木俊克
甲斐绫子
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Tokuyama Corp
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Tokuyama Corp
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Abstract

An aluminum nitride sintered compact comprises grains having an average grain diameter (D50) of 0.1 to 2.5 mum, has a pore area ratio of 1 X 10<-7> or less, has a pore density of 0.05 pieces/mm<2> or less with respect to pores having a diameter of 1 mum or more, and a Vickers hardness in the range of 14 to 17 GPa. The aluminum nitride sintered compact is comprised of grains having a relatively small diameter and has a markedly low pore density, and thus is excellent in strength characteristics and in the capability of being formed into a mirror surface and is useful, in particular, as a material for a circuit board having a surface on which a fine wiring pattern is formed.

Description

Aluminum nitride sintered product
Background of invention
(invention field)
The present invention relates to novel aluminum nitride sintered compact and manufacture method thereof.The present invention more specifically includes smaller grain-size crystal grain, contain very in a small amount hole, be particularly suitable for as polishing minute surface substrate and have high-intensity aluminum nitride sintered product.
(description of Related Art)
Because its excellent heat conductivility, insulating property and nontoxicity, aluminum nitride sintered product have obtained the practical application that has the thermal radiation function base material as various.
Up to now, produce aluminum nitride sintered product on technical scale, be by up to 1,700 ℃ or under the higher temperature always, and the aluminium nitride powder that has added sintering aid is therein carried out sintering (being referred to as the resistive heating sintering process in the back).
The resistive heating sintering process is to carry out sintering in the time of lengthening, and the crystal grain of aluminium nitride is just grown and constituted sintered compact in this process.Therefore, the sintered compact that obtains with aforesaid method has bigger grain-size.In addition, the gas of carrying secretly in the raw material aluminium nitride powder produces and forms more macroporous phenomenon along with crystal grain is grown together.
Therefore, when attempt to the sintered compact that obtains by above-mentioned resistive heating sintering process surface picture with it when carrying out mechanical workout the minute surface of circuit substrate, grain-size is big and have hole to exist all to make it be difficult to highly fine wiring pattern of formation.Again, thus general because grain-size and have hole to exist this sintered compact intensity little, even see also also have room for improvement from the viewpoint of intensity.
On the other hand, when making ceramic sintered bodies, being exposed to the method that reduces resulting sintered compact grain-size in the plasma body by the aluminium nitride powder that will add sintering aid is known (patent documentation 1:JP-A-2-172,869).
Aforesaid method can access the sintered compact with little grain-size.Yet when carrying out sintering, it is very crucial requirement that plasma gas infiltrates inside.In addition, sintering will be finished at short notice, and therefore, this gas tends to be captured in the sintered compact.As a result, though the method for patent documentation 1 can reach the more or less high sintered density of youngster, residual inevitably in sintered compact have a hole.The existence of hole makes and is difficult to this sintered compact is used as the substrate that requires to form height forming fine wiring pattern circuit.In addition, this method needs main equipment to produce and keeps plasma body, and this is difficult to problem that this method is implemented with regard to relating on technical scale.
On the other hand, proposed to utilize the method for making ceramic sintered bodies by the what is called " discharge plasma " of in to the ceramic powder compacting, sending into pulsed current in recent years.Particularly, the method for sintering ceramic powder in pressing mold has been proposed, promptly under the state that pressurizes between the electrode, use the ceramic powder filled pressing mold, add hot-die by sending into pulsed current, in ceramic powder, produce the method (patent documentation 2:JP-A-2000-128,648) of plasma body.
The sintering method of above-mentioned use discharge plasma is by adding hot-die, when improving temperature, using simple equipment to carry out.Therefore, can control temperature at an easy rate, so this method can be paid close attention to as the technology in future.In this way, further ceramic powder is heated to sintering temperature at short notice, has suppressed the growth of crystal grain in the agglomerating process, expection can access physical strength and compare with the resulting bigger sintered compact of common electrical resistance heating.
Yet, when being used for the sintered aluminum nitride powder, above-mentioned plasma discharging body method finds, formed a large amount of holes, though its size is all little than the hole that is obtained by the resistive heating sintering process.In other words, patent documentation 2 discloses by pre-treatment press ceramic powder densely, handles such as hydraulic pressure, is warming up to 300～1 by the input pulse electric current then, and 500 ℃, thus make the method for ceramic sintered bodies.Yet the inventor confirms, although compacting makes it to have enough big density to aluminium nitride powder, is difficult to avoid form hole in sintered compact.Therefore, on the aluminum nitride sintered product that method obtains thus, be difficult to form minute surface with height planeness.
Brief summary of the invention
Therefore, the purpose of this invention is to provide a kind of aluminum nitride sintered product that little grain-size crystal grain is arranged, contain very a spot of hole therein, and have big intensity and high specific conductance, the manufacture method of this sintered compact also is provided.
To achieve these goals, the inventor has carried out research and discovery with keen determination, when reaching when aluminium nitride powder carried out treatment temp, the pulsed current of sending into is set in the high value that can significantly not grow up to aluminum nitride grain, in the agglomerating process, just can remove the bubble in the powder effectively, thereby obtain having the very aluminum nitride sintered product of fine porosity density.Further find, carry out the aluminum nitride sintered product that sintering obtains, because its agglomerating mode and the high temperature that is reached demonstrate very big hardness, and show the common inaccessiable high rigidity characteristic of aluminum nitride sintered product by sending into pulsed current.
According to the present invention, provide a kind of aluminum nitride sintered product that crystal grain is arranged, its average grain size (D 50) be 0.1～2.5 μ m, interstitial surface area is not more than 1 * 10 -7, the void density that diameter is not less than 1 μ m hole is not more than 0.05 hole/mm 2, Vicker hardness is then in the scope of 14～17GPa.
According to the present invention, further provide a kind of and make the method for aluminum nitride sintered product by the sintered aluminum nitride powder by sending into pulsed current, wherein to being heated to above 1,500 ℃ but be not higher than and send into pulsed current when 1,800 ℃ aluminium nitride powder is suppressed.
According to the present invention, further provide a kind of substrate (circuit substrate) that is used for circuit by aluminum nitride sintered product being carried out mirror polish.
Aluminum nitride sintered product of the present invention comprises the crystal grain of little grain-size, contains seldom to measure the macrovoid that is not less than 1 μ m, can carry out excellent mirror polish.Therefore, by mirror polish, the planeness that aluminum nitride sintered product of the present invention just forms with excellence is the minute surface of feature.Therefore, aluminum nitride sintered product of the present invention is very useful as the circuit substrate that forms the fine circuitry pattern in the above, and very high industrial value is provided.
Have, aluminum nitride sintered product of the present invention has such as the characteristic of high surface hardness very again, in the application of base material, be easy to dispose, and in using, also be useful as other that require the heat conductivility sliding component.
Manufacture method according to aluminum nitride sintered product of the present invention, can access aluminum nitride sintered product with high surface hardness, this sintered compact is characterised in that superfine structure, narrow sintered compact grain size distribution, low void density and high surface hardness, and need not make compressing powder by CIP, perhaps any step need not be carried out in advance, such as the step of extra-fine grinding powder.
The accompanying drawing summary
Fig. 1 is the view that the basic structure of the equipment that uses in the manufacture method of the present invention schematically is described.
Detailed Description Of The Invention
(aluminum nitride sintered product)
Aluminum nitride sintered product of the present invention is characterized in that little crystallite dimension, and contains very in a small amount The macrovoid that is not less than 1 μ m. Therefore, when mirror finish is carried out on the surface, of the present invention Having that aluminum nitride sintered product has just obtained never to see in traditional aluminum nitride sintered product is excellent " surpassing " minute surface of different flatness.
In other words, aluminum nitride sintered product of the present invention, its average grain size (D50) be 0.1～2.5 μ m, pore area than little to 1 * 10-7Or littler (desirable pore area ratio is essentially 0), diameter be not less than the void density of hole of 1 μ m little to 0.05 hole/mm2Or littler (desirable hole Gap density is essentially 0).
In the present invention, the average grain size of aluminum nitride sintered product, pore area ratio and diameter are not Density less than the hole of 1 μ m is assumed to be value as described below.
(1) average grain size (μ m): D50
Diameter (D in grain size distribution curve accumulation 50%50), be equivalent to burn at aluminium nitride The diameter of the crystal grain roundel of finding on the high polishing surface on any section of knot body.
(2) void density (hole/mm2)
Be illustrated in by per unit on the resulting surface of any section of mirror finish aluminum nitride sintered product The value of the number of pores of area.
(3) interstitial surface area ratio
Calculate total void area divided by the observed resulting value of total visual field area by the diameter that on the aluminum nitride sintered product high polishing surface, pre-determines the hole that exists in the visual field in district (being not less than 1 μ m).
Narrate the details of measuring method in an embodiment.
If attempt to obtain of the present invention aluminum nitride sintered product of average grain size less than 0.1 μ m, just be subjected to oxidation to a great extent in reinforced stage aluminium nitride powder, the aluminum nitride sintered product that the result obtains demonstrates the thermal conductivity of reduction.On the other hand, average grain size but demonstrates the intensity of reduction above the aluminum nitride sintered product of 2.5 μ m.
When the diameter of aluminum nitride sintered product of the present invention is not less than the void density of 1 μ m hole greater than 0.05 hole/mm 2The time, make the minute surface machining property descend owing to have hole, be difficult to obtain the minute surface of high-flatness, sintered compact demonstrates the intensity of reduction simultaneously.
Have again, when aluminum nitride sintered product of the present invention has greater than 1 * 10 -7Interstitial surface area than the time owing to exist hole, even void density and little also makes the minute surface machining property reduce strength degradation.
The aluminum nitride sintered product that is obtained by traditional resistive heating sintering process is even the aluminium nitride powder that uses little grain-size as raw material, also makes crystal grain grow significantly.The size of this crystal grain surpasses 2.5 μ m as a result, often surpasses 5 μ m according to different situations.Even under the little situation of void density, the diameter of hole also can increase along with the growth of crystal grain, and the interstitial surface area on the section of aluminum nitride sintered product surpasses 5 * 10 than general -7Therefore should be appreciated that, can not obtain having little grain-size and the aluminum nitride sintered product of the present invention that contains a small amount of hole by traditional resistive heating sintering process.
Have again, aluminum nitride sintered product of the present invention with compare by traditional resulting aluminum nitride sintered product of resistive heating sintering process, it is characterized in that having very high hardness.In other words, aluminum nitride sintered product of the present invention demonstrates 14～17GPa, particularly the Vicker hardness of 14.5～16.5GPa.This value is 1.4 times of above-mentioned traditional aluminum nitride sintered product Vicker hardness.
Though make aluminum nitride sintered product of the present invention contain a small amount of hole and to demonstrate the mechanism of aforesaid high rigidity also fuzzy, it is envisaged that it is that the crystal grain of aluminium nitride grows into suitable degree and forms very fine and close structure in the smaller scope of grain-size.
In addition, aluminum nitride sintered product of the present invention because it has littler grain-size than the aluminum nitride sintered product that is obtained by traditional resistive heating sintering process, thereby demonstrates big intensity.Such as, demonstrate the flexural strength that is not less than 500MPa by also using sintering aid to carry out the aluminum nitride sintered product of the present invention that sintering obtains.
Have, the aluminum nitride sintered product of the present invention that obtains when not using sintering aid demonstrates the thermal conductivity up to 50～80W/mK again, and the thermal conductivity of the aluminum nitride sintered product that obtains when also using sintering aid to carry out sintering is up to 100W/mK.
In the present invention, the crystal grain that goes out to return special hope formation sintered compact from the further viewpoint of improving the mirror finish performance has following grain size distribution, makes that the difference between cumulative 90% grain-size and cumulative 10% grain-size is not more than 1.5 μ m.In the manufacture method of the present invention of using pulsed current as described below, crystal grain is almost not growth in the agglomerating process, and therefore the grain size distribution of used aluminium nitride powder just directly reflects.So, when the grain size distribution of regulating used aluminium nitride powder is the grain size distribution of above-mentioned crystal grain, just can be easily the grain size distribution of this crystal grain be adjusted in the above-mentioned scope.
Aluminum nitride sintered product of the present invention also can contain the as above sintering aid that is used for reducing fusing point of summary on grain surface except list is made of aluminium nitride.As sintering aid, use yttrium oxide (Y the most widely 2O 3).Yet, can use any known sintering aid, such as being used alone or in combination alkaline earth compound, such as CaO and SrO, perhaps rare earth compound is such as CeO 2, Ho 2O 3, Yb 2O 3, Gd 2O 3, Nb 2O 3, Sm 2O 3And Dy 2O 3
Have, when sending into pulsed current and make as passing through of will narrating below, aluminum nitride sintered product of the present invention can make in the lip-deep zone of oxidation of aluminium nitride powder and easily vaporize and decompose, and promptly obtains having the sintered compact that has reduced oxygen level again.
(manufacturing aluminum nitride sintered product)
Narrate the manufacture method of aluminum nitride sintered product of the present invention below.
In other words,,, make its temperature that reaches be higher than 1,500 ℃ but be not higher than 1,800 ℃, so just make aluminium nitride sintered product with above-mentioned performance by sending into pulsed current sintered aluminum nitride powder in compacting according to the present invention.
The average grain size that the preferred aluminium nitride powder that uses has is slightly smaller than the average grain size of sintered compact as mentioned above.More specifically say, wish the aluminium nitride powder of use, its average grain size is at 0.05～5 μ m, and is special in the scope of 0.1～1 μ m.In other words, when average crystal grain diameter during less than 0.05 μ m, the ratio of zone of oxidation increases on grain surface.And on the other hand, when average grain size was not more than 5 μ m, it is very big that grain-size becomes, and can not get intensity, and the void density compacting is low-level less than one.In other words, be difficult to obtain having the aluminum nitride sintered product of excellent mirror finish performance.
The purity of wishing aluminium nitride powder is not less than 97wt%, particularly is not less than 99wt%.Highly purified aluminium nitride powder like this is arranged in market, can obtain easily.
Aforesaid sintering aid can be sneaked in the above-mentioned aluminium nitride powder and use.The viewpoint that obtains bigger thermal effectiveness after sintering that will narrate from below is set out, and wishes to use sintering aid.The aluminium nitride powder of per 100 weight parts wishes that the amount of the sintering aid of use is 0.1～10 weight part, especially 1～5 weight part.
According to the present invention, in to aluminium nitride powder (or mixed powder of AlN powder and sintering aid) compacting, come sintered aluminum nitride by sending into pulsed current.In other words, send into pulsed current, the electric energy of pulse type is directly delivered in the gap between the powder grain, thus will be owing to spark discharge the high-energy of the high-temperature plasma of instantaneous generation put on thermodiffusion/electric field diffusion effectively, forming partial necking down effectively in crystal grain connects, arrive then necking down is connected grow into and stablize the thermal equilibrium state that connects, thereby in the short time, just realized sintering.According to this pulse current method (often being called as the discharge plasma sintering process), can obtain not having the high-density sintered body of hole at short notice, keep high quality simultaneously, although there is the sintering aid that is used on grain surface reducing fusing point to exist, under high temperature, can not allow the crystallization hypertrophy at low temperature.
In view of in pressurization, sending into pulsed current, just aluminium nitride powder is encased in the die space between a pair of compacting drift of making by conductive carbon that is inserted into by the pressing mold of conductive carbon manufacturing with from top side and bottom side the pressing mold.By suppressing drift in of the aluminium nitride powder compacting of both sides, the end, top, send into dc pulse current by the compacting drift to adding like this.
The current density of pulsed current is generally 150～500A/cm 2, be preferably 300～400A/cm 2, the recurrence interval is 30Hz～30kHz, is preferably about 100Hz to about 10kHz.Useful again electric current break time (closing) was generally about 1: 1～about 2: 24 with the ratio of pulse length to the total cycle length (closing: open) that the ratio of electric current time of setting up a call (opening) is represented, was preferably about 1: 6～about 2: 12, and voltage is 1～10V, is preferably 2～6V.
Further wish in a vacuum or in inert gas atmosphere, feed pulsed current.Also allow when sending into pulsed current, add the hot-die electric current and carry out boosting by sending into dividually.
When sending into pulsed current, wish that the pressure of compacting aluminium nitride powder is 0.3～0.6tf/cm 2, 0.35～0.45tf/cm particularly 2When pressure less than 0.3tf/cm 2The time, it is fine and close that aluminium nitride powder does not become.In other words, sintered density can not increase, and while void density and interstitial surface area ratio tend to increase.On the other hand, surpass 0.6tf/cm when pressure 2The time, sintering carries out easily, but the effect that density increases has then reached the limit, and the agglomerating instrument, such as the possibility increase of pressing mold and the damage of compacting drift.
Have again, it is important, send into temperature that pulsed current reaches, preferably be not less than 1,550 ℃ to not being higher than 1,800 ℃ for being higher than 1,500 ℃ to not being higher than 1,800 ℃ scope.In other words, when the temperature that reaches is lower than 1,500 ℃, in sintering step, just can not fully remove the gas of deentrainment.Therefore, the total amount of hole does not reduce, and void density and interstitial surface area are discontented with the unabridged version scope of invention than all, and this just can be clear that in the embodiment of back.Have, when the temperature that reaches surpassed 1,800 ℃, the crystal grain in sintered compact was grown significantly, has reduced minute surface machining property and intensity again.
The thermometer that is reached is shown in the top temperature when sending into pulsed current and set up discharge plasma.In the temperature that is reached, send into pulsed current continuously or carry out boosting continuously, to keep said temperature, obtain having the fine porosity density of keeping stability and the aluminum nitride sintered product of fine porosity area ratio thus until finishing sintering.Though have no particular limits, the time of keeping said temperature generally is 1～30min, is preferably 1～5min.Can regulate the temperature that is reached by the intensity of interval between regulating impulse current's intensity, the pulse and boosting power supply.
Wish also that in addition with 30～150 ℃/min, the heat-up rate that is preferably 50～100 ℃/min reaches this temperature.When heat-up rate was slow, temperature curve was just elongated.When heat-up rate is too fast, just be difficult to obtain enough fine and close sintered compact.
In above-mentioned manufacture method, when packing aluminium nitride powder into pressing mold, wish carbon plate of insertion on aluminium nitride powder and interface that this equipment contacts, between the sintered compact avoiding to obtain and the pressing mold sintering to take place.
The aluminum nitride sintered product that so obtains is a characteristic with the minute surface machinability of excellence, can form very smooth minute surface (is 0.04 μ m or littler such as the maximum surfaceness Rmax that has) by mirror polish, and demonstrates excellent intensity.Yet,, tend to demonstrate low slightly thermal conductivity at this aluminum nitride sintered product because grain-size is little.Therefore, according to the present invention, after interrupting sending into pulsed current, the sintered compact that hope will obtain by above-mentioned sintering step 800 ℃, preferably 1,680～1, is heat-treated under 780 the temperature 1,550～1.By above-mentioned thermal treatment, aluminum nitride sintered product demonstrates the thermal conductivity of remarkable improvement and can not damage above-mentioned performance.When thermal treatment temp was lower than 1,550 ℃, improved thermal conductivity was less than enough degree.When thermal treatment temp surpasses 1,800 ℃, grain growing, sintered compact demonstrates the flexural strength of reduction.
By above-mentioned thermal treatment, the crystal grain continued growth, and the void density of while sintered compact and interstitial surface area ratio still keep almost constant, the minute surface machinability can not reduce.Therefore, thermal treatment must be at the average grain size (D of sintered compact 50) carry out under the condition in above-mentioned scope.For this purpose, wish that heat treatment time (sintered compact remains on the time under the thermal treatment temp) is 1～15h, especially at 3～10h.When heat treatment time is shorter than 1h, do not make improved thermal conductivity arrive enough degree.When heat treatment time surpassed 15h, grain growing reduced intensity.
After no longer sending into pulsed current, by the boosting of pressing mold etc. is come the maintenance heat treatment temp.
Just as has been described, particularly when sintering aid uses with aluminium nitride powder, can also improve thermal conductivity by thermal treatment.When thermal treatment will be finished in the short period of time, wish to use sintering aid.
Fig. 1 schematically illustrates to implement the preferably view of the basic structure of use equipment of the inventive method institute.
Referring to Fig. 1, this equipment is equipped with the pressing mold of being made by conductive carbon, and a pair of compacting drift 2 by the conductive carbon manufacturing that is assembled in the pressing mold 1 also is housed.In the middle of pressing mold 1, add aluminium nitride powder 3, send into dc pulse current by compacting drift 2, temperature is elevated to preset value (sintering temperature), use drift 2a from both sides, the end, top compacting adding powder wherein simultaneously, after reaching sintering temperature, keep this temperature preset time, to form sintered compact.
Use the controlling organization that does not show, exert pressure, and send into pulsed current by compacting drift 2 by compacting drift 2.
As requested, aforesaid device is installed in the chamber 4, uses vacuum pump 5 that 4 inside, chamber are vacuumized.Also allow to carry out sintering when substituting the inside of chamber 4 using such as nitrogen.
In the time of in pressing mold 1 that aluminium nitride powder is packed into, hope is at the internal surface of the pressing mold 1 that contacts with powder and place a carbon plate (or carbon film) on the surface of compacting drift 2, to prevent between aluminium nitride powder and above-mentioned surface sintering taking place.
Embodiment
Narrate embodiment below, the sacrificial vessel body illustrates method of the present invention, yet this just illustrates the present invention, never in any form it is construed as limiting.
Among below the embodiment and comparative example, each physicals is measured with method as described below.
1) metering orifice gap density
A section of sintered compact is carried out mirror polish.Use scanning electronic microscope (SEM), amplifying 1,000 times of bright finished surface of observation down, number goes out hole (diameter is not less than the cavity of 1 μ m) number.Amplifying 500 visuals field that are no less than of observing high polishing surface on 1,000 times the visual field, and the diameter of unit surface to be not less than the number of pores of 1 μ m be exactly void density.
2) interstitial surface area ratio
Diameter by the hole that goes out with method number as mentioned above calculates interstitial surface area, obtains the total area of the hole that is detected.The ratio of the total area of hole and observed total visual field area (being no less than 500 visuals field under amplifying 1,000 times) is exactly the interstitial surface area ratio.
3) loose density of measurement aluminum nitride sintered product
Measure according to the Achemedes method, calculate relative density.
4) grain-size of aluminium nitride
Use image analysis system (morning sun changes into the IP-1000PC that industry (strain) is made),, obtain grain-size from the microstructure photo of sintered compact with method as described below.
At first, any section to be estimated is finished to minute surface, and handles 1h under can not grow at aluminum nitride grain 1,600～1,650 ℃.By this processing, it is bigger than other parts that the corrosion speed of grain boundary becomes.Therefore, have only the grain boundary to be corroded, and obtain to identify each aluminum nitride grain and the grain boundary surface of crystal grain mutually thereon.
Then, use scanning electronic microscope (SEM) to observe this surface, in a visual field, comprise under the magnification of 200～300 observed crystal grain and take the microstructure photo, take multiple pictures to cover 1,000～2,000 observed crystal grain.The microstructure photo shows that the aluminium nitride crystalline particle is that ash arrives black, and shows that the crystal grain of grain boundary phase is white, so just makes crystal grain easily to differentiate out.
At last, the auxiliary image analysis system that uses a computer, the image from the microstructure photo obtains and 1,000～2,000 suitable diameter of aluminum nitride grain round.Further from obtaining corresponding to the grain boundary diameter of crystal grain round mutually with the similar microstructure photo of aluminum nitride grain.Aluminum nitride grain and grain boundary mutually crystal grain all be bordering on equiaxial, can be with representing grain-size with the corresponding diameter of this round.When analyzing, the crystal grain that is cut open at the end of analysis image is not included among the result of estimation.Further, when two or more grain boundaries phase crystal grain contact, and when the length of these two grain boundaries during greater than the average grain size of crystal grain, these two crystal grain are just regarded independent crystal grain together and are handled.
Based on measured crystal grain diameter distribution curve, obtain 10% accumulated value (D 10), 50% accumulated value (D 50) and 90% accumulated value (D 90), and calculate D 90And D 10Between poor.
5) measure surface roughness (JIS B0601)
To wait that the section of estimating sintered compact carries out mirror polish, use surfaceness and profile measuring machine (Surfcom478A that Tokyo precision (strain) is made) to measure its maximum surfaceness (Rmax).Measuring condition comprises cutting 0.8, speed of detection 0.06mm/sec, amplifies 50,000 times, measures length 0.25mm, obtains the mean value of 6 measurement point.
6) measure thermal conductivity
Measurement is based on the laser flash burn method of the thermal constant metering facility PS-7 that uses Rigaku electric (strain) to make.Use calibration curve that thickness is proofreaied and correct.
7) measure flexural strength
Under the pinblock speed of 0.5mm/min, according to JIS R1601, but span changes 20mm into, and test block thickness changes into and carries out the three-point bending test under the condition of 2mm.The width of test block is 4mm.Sintered compact is cut into the width of 6mm, and the width that 1mm obtains being scheduled to is cut off at two ends.Cut out upper and lower surface.
8) Vicker hardness
The AVKCO Vicker hardness-testing device that at room temperature uses the rising sun (strain) to make is measured, load 5kg, loading time 15sec.
9) average grain size of aluminium nitride powder
Use Microtrack 11 (LEED﹠amp; NORTHRUP company), by aluminium nitride powder is dispersed in the water, test based on laser diffractometry.
(embodiment 1)
(surface hardness is not more than 100kgf/mm will to be coated with the nylon ball of the diameter 15mm that iron core obtains with nylon 2, density 3.5g/cm 3) drop in the nylon jar of volume 2.4L.Add 100 weight part aluminium nitride powders in the nylon jar again, its average grain size is 1.3 μ m, specific surface area 3.39m 2/ g, oxygen level 0.8wt% also adds 40 parts by weight of ethanol as solvent, then they is carried out wet mixing together and closes.The add-on of nylon ball accounts for 40% of tank volume (apparent volume).Rotational speed nylon jar mixing 3h with 70rpm.The slurries that obtain are carried out drying, obtain aluminium nitride powder.
Then, use this aluminium nitride powder of equipment sintering of its basic structure of expression in Fig. 1.Pressing mold 1 and compacting drift 2 are all made with graphite.When adding aluminium nitride powder 3, on the stamping surface of compacting drift, cover carbon plate, to avoid suppressing the bonding between drift and the powder to obtain by even coating boron nitride powder.Use vacuum pump 5 that the inside of chamber 4 is vacuumized (reduced pressure).Further provide a control device (not shown) to control the output of sintering power supply, make the detected powder temperature of temperature sensor (not shown) that is arranged in pressing mold meet predefined temperature characteristics.Also control driving press driving mechanism and vacuum pump by this control device.
Send into pulsed current by the pressing mold drift, raise the temperature to sintering temperature, press driving mechanism action simultaneously makes the compacting drift be suppressed powder by both sides, the end, top.After reaching sintering temperature, keep this temperature preset time, mold pressing goes out sintered compact.
The most of electric current that the feeds head punch electrode → head punch → pressing mold → end drift → end drift electrode of flowing through produces Joule heat, is used for from outer survey heating powder.Remaining electric current flow through powder and flashing discharge in the gap of powder grain.The discharge plasma that spark discharge produces uses its high-energy to carry out thermodiffusion/electrolysis diffusion, and powder grain just combines securely according to anticipation.
Compacting drift 2 is from the compacting of both sides, the end, top, and its pressing force is 0.4tf/cm 2, apply the surface that pulsed voltage (impulsive condition is out: close=12: 2) adds hot-die and compacting drift.The speed of Sheng Wening is 100 ℃/min in a vacuum, and sintering temperature (temperature that the is reached) 5min that keeps 1,600 ℃ carries out sintering, is not less than 95% to obtain relative density, diameter 30mm, the sintered compact of thickness 3mm.
Table 1 demonstrates the condition of making aluminum nitride sintered product, and table 2 demonstrates the performance of the aluminum nitride sintered product that obtains.
(embodiment 2)
Operate similarly to Example 1, just selecting sintering temperature (temperature that is reached) is 1,780 ℃.
Table 1 demonstrates the condition of making aluminum nitride sintered product, and table 2 demonstrates the performance of the aluminum nitride sintered product that obtains.
(embodiment 3)
Operate similarly to Example 1, just selecting pressing pressure is 0.35tf/cm 2
Table 1 demonstrates the condition of making aluminum nitride sintered product, and table 2 demonstrates the performance of the aluminum nitride sintered product that obtains.
(embodiment 4)
Operate similarly to Example 1, just selecting pressing pressure is 0.55tf/cm 2
Table 1 demonstrates the condition of making aluminum nitride sintered product, and table 2 demonstrates the performance of the aluminum nitride sintered product that obtains.
(embodiment 5)
Operate similarly to Example 1, just selecting heat-up rate is 30 ℃/min.
Table 1 demonstrates the condition of making aluminum nitride sintered product, and table 2 demonstrates the performance of the aluminum nitride sintered product that obtains.
(embodiment 6)
Operate similarly to Example 1, just selecting heat-up rate is 140 ℃/min.
Table 1 demonstrates the condition of making aluminum nitride sintered product, and table 2 demonstrates the performance of the aluminum nitride sintered product that obtains.
(embodiment 7)
Operate similarly to Example 1, just be not less than 99.99%, specific surface is 12.5m by in the aluminium nitride powder of 100 weight parts, adding purity 2The 5 weight fraction yttrium oxide powders of/g prepare slurries.
Table 1 demonstrates the condition of making aluminum nitride sintered product, and table 2 demonstrates the performance of the aluminum nitride sintered product that obtains.
(embodiment 8)
Operate obtaining sintered compact similarly to Example 7, just add the sintering aid of 3 weight parts.
Table 1 demonstrates the condition of making aluminum nitride sintered product, and table 2 demonstrates the performance of the aluminum nitride sintered product that obtains.
(embodiment 9)
Operate obtaining sintered compact similarly to Example 7, just selecting sintering temperature (temperature that is reached) is 1,780 ℃.
Table 1 demonstrates the condition of making aluminum nitride sintered product, and table 2 demonstrates the performance of the aluminum nitride sintered product that obtains.
(embodiment 10)
Operate obtaining sintered compact similarly to Example 7, just selecting pressing pressure is 0.35tf/cm 2
Table 1 demonstrates the condition of making aluminum nitride sintered product, and table 2 demonstrates the performance of the aluminum nitride sintered product that obtains.
(embodiment 11)
Operate obtaining sintered compact similarly to Example 7, just selecting pressing pressure is 0.55tf/cm 2
Table 1 demonstrates the condition of making aluminum nitride sintered product, and table 2 demonstrates the performance of the aluminum nitride sintered product that obtains.
(embodiment 12)
Operate obtaining sintered compact similarly to Example 7, just selecting heat-up rate is 30 ℃/min.
Table 1 demonstrates the condition of making aluminum nitride sintered product, and table 2 demonstrates the performance of the aluminum nitride sintered product that obtains.
(embodiment 13)
Operate obtaining sintered compact similarly to Example 7, just selecting heat-up rate is 140 ℃/min.
Table 1 demonstrates the condition of making aluminum nitride sintered product, and table 2 demonstrates the performance of the aluminum nitride sintered product that obtains.
(embodiment 14)
Be that the sintered compact that will obtain in embodiment 7 carries out the thermal treatment of 2h under 1,750 ℃ the condition in temperature.
The aluminum nitride sintered product that obtains has and is bordering on same void density and interstitial surface area ratio, but grain-size is increased and thermal conductivity is brought up to 155W/mK (performance of the aluminum nitride sintered product that obtains is presented in the table 2).
(comparative example 1)
Operate similarly to Example 1, the temperature of just selecting to reach (sintering temperature) is 1,400 ℃.
Table 1 demonstrates the condition of making aluminum nitride sintered product, and table 2 demonstrates the performance of the aluminum nitride sintered product that obtains.
(comparative example 2)
Operate similarly to Example 1, the temperature of just selecting to reach (sintering temperature) is 1,200 ℃.
Table 1 demonstrates the condition of making aluminum nitride sintered product, and table 2 demonstrates the performance of the aluminum nitride sintered product that obtains.
(comparative example 3)
Operate similarly to Example 7, the temperature of just selecting to reach (sintering temperature) is 1,400 ℃.
Table 1 demonstrates the condition of making aluminum nitride sintered product, and table 2 demonstrates the performance of the aluminum nitride sintered product that obtains.
(comparative example 4)
Operate similarly to Example 7, the temperature of just selecting to reach (sintering temperature) is 1,200 ℃.
Table 1 demonstrates the condition of making aluminum nitride sintered product, and table 2 demonstrates the performance of the aluminum nitride sintered product that obtains.
(comparative example 5)
In the nylon jar that a volume is 10L, add nylon ball.The aluminium nitride powder that adds 100 weight parts in this nylon jar again, its average grain size are 1.5 μ m, and specific surface area is 2.6m 2/ g, oxygen level is 0.8wt%, and the yttrium oxide powder that also adds 5 weight parts is as sintering aid, and its specific surface area is 12.5m 2/ g also adds 0.5 weight fraction, six Rylo MG 19s as tensio-active agent, also adds the toluene of 3 weight fraction n-butyl methylacrylic acids and 100 weight parts, uses ball mill that they are mixed 24h then and makes it to mix, and obtains the slurries of white.The slurries granulation of using spray-drying process so to obtain obtains the aluminum nitride particle of diameter 70～100 μ m.
At 1.0tf/cm 2Pressing pressure under this particle is carried out mold pressing, obtain moulded body.Then in 600 ℃ air with this moulded body dewaxing 5h, and in boron nitride receptacle in 1,800 ℃ nitrogen atmosphere sintering 5h, obtain relative density and be not less than 95% sintered compact.
Table 1 demonstrates the condition of making aluminum nitride sintered product, and table 2 demonstrates the performance of the aluminum nitride sintered product that obtains.
(comparative example 6)
Operate equally with comparative example 5, just do not add sintering aid.Table 1 demonstrates the condition of making aluminum nitride sintered product, and table 2 demonstrates the performance of the aluminum nitride sintered product that obtains.
Figure C0382529600191
Figure C0382529600201
Figure C0382529600211
Aluminum nitride sintered product of the present invention contains very a spot of hole and has high rigidity, therefore can be used as the base material of making the high precision wiring pattern by the surface mirror mirror polish.Such as, this sintered compact is carried out mirror polish and obtains having the circuit substrate of surfaceness Rmax less than the very smooth minute surface of 0.04 μ m.In addition, because this aluminum nitride sintered product has high rigidity and high thermal conductivity, it can be used as the slide unit that can give off heat of friction effectively.

Claims (6)

1. aluminum nitride sintered product, this sintered compact contains average grain size D 50Be the crystal grain of 0.1～2.5 μ m, have and be not more than 1 * 10 -7The hole area ratio, and the hole density that diameter is not less than the hole of 1 μ m is not more than 0.05 hole/mm 2, its Vicker hardness is 14～17GPa simultaneously, the grain size distribution of wherein said crystal grain makes at the grain-size D of accumulation 90% 90Grain-size D with accumulation 10% 10Between difference be not more than 1.5 μ m.
2. make the method for the aluminum nitride sintered product of claim 1 by sending into the pulse electric current sintering aluminium nitride powder for one kind, wherein in to the aluminium nitride powder compacting, send into pulsed current, make the temperature that reaches be higher than 1,500 ℃, but be not higher than 1,800 ℃, and the pressure of wherein aluminium nitride powder being suppressed is not less than 0.3tf/cm 2, but less than 0.6tf/cm 2, the heat-up rate that wherein is warming up to the temperature that reaches be 30～150 ℃/min and wherein the average grain size of aluminium nitride powder be 0.05～5 μ m.
3. make the method for aluminum nitride sintered product according to claim 2, wherein under vacuum or in inert gas atmosphere, carry out sintering.
4. make the method for aluminum nitride sintered product according to claim 2, wherein after interrupting sending into pulsed current, the sintered compact that obtains 1,550～1, is heat-treated under 800 ℃ the temperature.
5. make the method for aluminum nitride sintered product according to claim 2, wherein aluminium nitride powder is mixed with sintering aid, the aluminium nitride powder of per 100 weight parts mixes 0.1～10 weight part sintering aid.
6. one kind is carried out the substrate that mirror polish obtains by the aluminum nitride sintered product with claim 1.
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